Nitrated pentaerythritol motherliquor



Patented Mar. 28, 1939 2,152,372

NITRAT'ED PENTAEBYTHRITOL MOTHER- LIQUOR Joseph A. Wyler, Allentown, Pa., assignor to Trojan Powder Company, Allentown, Pa.

No Drawing. Application November 4, 1938,

Serial No. 238,804

11 Claims. (01. 52-5) This invention relates to a composition of matcontains less than a substantial amount of pentater and to a process for the preparation thereof. e yth d p ta q and 15 therefore More specifically, it relates to the nitrated proddiscarded by the commercial manufacturers of not obtained by the nitration of the liquid end- De tae yt as a Worthless -p 5 product formed during the commercial prepara- I have discovered that, contrary to the general 5 tion of pentaerythritol by the alkaline condensaimpressio ve in t literature, this y p y tion of formaldehyde and acetaldehyde. be nitrated to form a nitrated productuseful in An object of this invention is to convert a the explosives industry. hitherto worthless by-product into a material of This sy up, as it exists immediately after the value in the explosives industry. separation of the pentaerythritol and the diii A further object is to provide a new liquid expentaerythritol is usually of a brownish color plosive of certain unusual properties which are and consists of water, formic acid, acetic acid, disclosed in a later part of this specification. methyl alcohol, ethyl alcohol, formates, aide- A still further object is to provide explosive hydic or ketonic substances, compounds possesscompositions in which this new nitrated product ing the primary alcohol group or groups 15 is associated with other nitrated explosives, oxi- (--CHzOH), and/or secondary alcohol groups dizing agents, oxidizable agents, heat producing (=CHOH), probably some formose, other polyagents, density modifying agents and other hydroxy substances, as well as other unknown agents for causing changes in the character and substances.

condition of explosive mixtures. This syrup is freed of most of its moisture and 20 Other objects of this invention will become ap-' volatile constituents by any suitable method, such parent upon further perusal of this specification. as vacuum distillation, vacuum drum drying, etc.

The commercial preparation of pentaerythritol after which it is in the form of a very viscous is based upon the reaction of one molecule of, liquid ready for nitration.

acetaldehyde upon 4 molecules of formaldehyde, The nitration of this liquid may be carried out 25 such reaction taking place in the presence of 4 by means of concentrated nitric acid alone, a to 5 molecules of formaldehyde for each molecule mixture of concentrated nitric acid and sulphuric of acetaldehyde, in alkaline medium, and in such acid, a mixture of concentrated nitric acid and a volume of water as to provide a solution conphosphoric acid or, in general, a mixture of nitric taining less than 20% of aldehydes at the beginacid and a dehydrating agent. 30 ning of the reaction. In order to more clearly point out how I nitrate- The main reaction may be represented as folthis product, the following examples are given. lows: Example #1 v p 4CHZO+CH3CHO+MOH= 1 part, by weight, of this dried syrup is added 35 +M9 slowly, with stirring, to 10 parts, by weight, of where M equals a univaient metal or one-half 95% HNO3 contained in a suitable vessel. The. of a bivalent metal. temperature is kept below 30 C. When all of In these commercial processes the alkali used the syrup has been added, the mixture will have 40 for the condensation is Ca(OH):, B8.(OH)2, or a milky appearance and practically all of the 40 NaOH. Consequently, after the condensation itnitrated product will be in solution in the excess S the p y lt must be Separated from of nitric acid. Stir for an additionalhalf hour. a metal formate and other products. Usually. Then allow the contents of the nitrator to flow this is done by r in the m x ure after the into about three times its volume of cold water, densation react o With Sulphuric a OXelie as the mixture is being stirred. This precipitates 45 acid 01 both, to precipitate the C8, 01 Ba ions as the nitrated product in the form of a syrup, or sulfate or oxalate. The insoluble Ca or Ba salts hi h i allowed to p t t and is are Separated y filtration, leaving the D then given several waterlwashes oneor more ry hritol, formic acid, and various bar-prod washes with a'dilute aqueous solution of sodium in solution. carbonate, sodium .bicarbonate disodiumphos- 50 The solution thus formed is subjected to rephate or any other's'uitable, base, and isfthen peated evaporations and crystallizations in order llowed to settle so as to become fairly dry. t s pa a the p ta t l and th d p This viscous layer, which isthelimpure 'nitrated erythritol (formed by a side reaction) from a roduct, may then be dissolved in a solvent, such sy upy p ll iyr py product usually as acetone and the solution treated with a slight excess of ammonium carbonate or other suitable alkali in order to neutralize all free acid which may be present in the solution. The alkaline mixture is stirred for a half hour or more in order to insure complete neutralization of any free acid which may be present and thus to further stabilize the nitrated product.

This alkaline solution is then treated with water in order to cause the precipitation of the nitrated product and to cause the substantial removal of the acetone from this nitrated material. After several water washes, combined with settling at room or slightly elevated temperatures, this viscous, nitrated product is ready for use in the explosives industry.

Example #2 1 part, by weight, of the dried syrup is slowlyadded to about 8 parts by weight of 95% HNOs contained in a nitrating vessel. The mixture is thoroughly stirred and cooled to below 30 C. When all of the syrup has been added, about 5 parts by weight of concentrated sulphuric acid are slowly added, keeping the temperature low.

The mixture is stirred for one-half to one hour or more, is then drowned in a large volume of cold water and then handled in essentially the same manner as under Example #1. The nitrated product after drying contained 12.87% N and was practically colorless.

It will, of course, be apparent to a person skilled in this art that many modifications and alterations may be made in the methods given in the examples without departing from the spirit of this invention.

The nitration product made in accordance with my disclosure is a new and useful composition of matter. Its nitrogen content, determined by means of the nitrometer, is at least 12.50% N. It is an explosive and remains liquid or viscous to temperatures below the freezing point of water. It possesses satisfactory stability toward heat. It is soluble in acetone, ether, ethylene dichloride, benzene, toluol, chloroform and tetrachlorethane. It is rather difiicultly soluble in methyl alcohol, ethyl alcohol and propyl alcohol; and insoluble in propane, pentane, and carbon tetrachloride.

It possesses the unexpected properties of being soluble in benzene and of being a non-solvent for nitrostarch in the cold, and also of either having by itself alone or in combination with a small proportion of benzene, appreciable solvent effect upon rubber. Furthermore, it is non-headache producing and possesses a very low volatility.

My nitrated product is an explosive and may be used alone or it may be used in association with other nitrated products as nitrostarch, ni-

trocellulose, nitroglycerin, nitrated sugar, pentaerythritol tetranitrate, nitrated glycols, nitrotoluenes, and the like; with oxidizing materials as ammonium nitrate, sodium nitrate, potassium nitrate, potassium perchlorate, and ammonium perchlorate; with oxidizable agents as charcoal, coal, wood pulp, vegetable ivory, bagasse, oils and other carbonaceous materials; with heat producing agents as powdered aluminum, ferrosilicon, and metallic silicon; and with modifying agents as sodium chloride, sodium bicarbonate, ammonium oxalate, zinc oxide, rubber and the like.

It will be apparent to those versed in the explosives art that my invention comprehends not only free-flowing, but also plastic and waterproof explosives, and that my new explosive has usefulness as a waterproofing, anti-caking, and

ing after the separation of the pentaerythritols from the reaction mixture produced in the commercial pentaerythritol alkaline condensation of formaldehyde and acetaldehyde, comprising the treatment of this syrup with a nitrating acid at a temperature below 30 C.

2. The process of nitrating the syrup remaining after the separation of pentaerythritols from p the reaction mixture produced in the commercial pentaerythritol alkaline condensation of formaldehyde and acetaldehyde, comprising the treatment of this syrup with concentrated nitric acid at a temperature below 30 C.

3. The process of nitrating the syrup remaining after the separation of pentaerythritols from the reaction mixture produced in the commercial pentaerythritol alkaline condensation of formaldehyde and acetaldehyde, comprising the addition of about 1 part by weight of this syrup to about 8 parts by weight of 95% HNOz, followed by the addition of about 5 parts by weight of oil of vitriol, below 30 0., and then drowning the nitrated charge in an excess of water.

4. The process of nitrating the syrup remaining after the separation of pentaerythritols from the reaction mixture produced in the commercial pentaerythritol alkaline condensation of formaldehyde and acetaldehyde, comprising the addition of about 1 part by weight of this syrup to about 8 parts by weight of 95% HNOa, followed by the addition of about 5 parts by weight of oil of vitriol, below 30 C., and then drowning the nitrated charge in an excess of water, washing, neutralizing with an alkaline solution, separating from water, dissolving the gum in acetone, neutralizing again, and then treating this acetone solution with water in order to precipitate the nitrated syrup substantially free from acetone.

5. The nitrated product resulting from the ni-' tration of the substantially pentaerythritol-free syrup produced in the commercial alkaline condensation of formaldehyde and acetaldehyde.

6. The syrupy nitrated product resulting from the nitration of the substantially pentaerythritol-free syrup produced in the commercial alkaline condensation of formaldehyde and acetaldehyde.

7. The syrupy nitrated product resulting from the nitration of the substantially pentaerythritol-free syrup produced in the commercial alkaline condensation of formaldehyde and acetaldehyde and containing at least 12.50% N when dry.

8. An explosive comprising the syrupy nitrated product resulting from the nitration of the substantially pentaerythritol-free syrup produced is the commercial alkaline condensation of formaldehyde and acetaldehyde.

9. An explosive comprising the syrupy nitrated product resulting from the nitration of the substantially pentaerythritol-free syrup produced in the commercial alkaline condensation of formaldehyde and acetaldehyde, and nitrostarch.

10; An explosive comprising the syrupy nitrat- 11. An explosive comprising the syrupy nitrat ed product resulting from the nitration of the ed product resulting from the nitration of the substantially pentaerythritol-free syrup prosubstantially pentaerythritol-free syrup produced in the commercial alkaline condensation duced in the commercial alkaline condensation of formaldehyde and acetaldehyde, nitrostarch of formaldehyde and acetaldehyde. and rubber. 5 Q I and anoxidizing salt. JOSEPH A. WYLER. 

